Aqueous binders for granular and/or fibrous substrates

ABSTRACT

This invention relates to an aqueous binder composition containing a) at least one polymer P and b) at least one saccharide compound S, such that an amount of the saccharide compound S is ≧10 and ≦400 parts by weight per 100 parts by weight of polymer P, wherein an amount of an additional formaldehyde-containing binder is ≦50 parts by weight per 100 parts by weight of the summed overall amounts of the polymer P and the saccharide compound S. This invention also relates to a process for producing a shaped articles from granular and/or fibrous substrates where an aqueous binder composition of the present invention is applied to the granular and/or fibrous substrate, the granular and/or fibrous substrate thus treated is optionally shaped and then the granular and/or fibrous substrate thus obtained is thermally treated. This invention also relates to shaped articles obtained by a process of the present invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. application Ser. No.13/437,174, filed on Apr. 2, 2012, which is a Non-Provisional of U.S.Provisional Application No. 61/471,228 filed on Apr. 4, 2011.

BACKGROUND OF THE INVENTION

The present invention relates to an aqueous binder compositioncomprising, as essential binder components,

-   a) at least one polymer P constructed from    -   ≧0.1 and ≦15 wt % of at least one acid-functional ethylenically        unsaturated monomer and/or at least one α,β-monoethylenically        unsaturated C₃ to C₆ mono- or dicarboxamide (monomers A)    -   ≧8.0 and ≦30 wt % of at least one ethylenically unsaturated        carboxylic acid nitrile or dinitrile (monomers B)    -   ≧0 and ≦5.0 wt % of at least one crosslinking monomer having two        or more nonconjugated ethylenically unsaturated groups (monomers        C)    -   ≧0 and ≦10 wt % of at least one monoethylenically unsaturated        silane compound (monomers D)    -   ≧20 and ≦70 wt % of at least one ethylenically unsaturated        monomer whose homopolymer has a glass transition temperature        ≦30° C. (monomers E) and which differs from the monomers A to D,        and    -   ≧25 and ≦71.9 wt % of at least one ethylenically unsaturated        monomer whose homopolymer has a glass transition temperature        ≧50° C. (monomers F) and which differs from the monomers A to D,        -   in polymerized form, wherein the amounts of monomers A to F            sum to 100 wt %, and-   b) at least one saccharide compound S, the amount of which is    determined such that it is ≧10 and ≦400 parts by weight per 100    parts by weight of polymer P, and    where the overall amount of additional formaldehyde-containing    binder components is ≦50 parts by weight per 100 parts by weight of    the summed overall amounts of polymer P and saccharide compound S.

The present invention further relates to the use of the aforementionedaqueous binder composition as binder for granular and/or fibroussubstrates, processes for production of shaped articles by using theaqueous binder composition and also to the shaped articles thusobtained, more particularly bonded fiber webs which in turn are used forproducing bituminized roofing membranes.

Polysaccharide-containing aqueous binder compositions must be viewed inlight of the following prior art:

EP-A 649 870 discloses mixtures of polycarboxylic acids and saccharidecompounds in a weight ratio ranging from 95:5 to 20:80 for production ofgas barrier films.

EP-A 911 361 discloses aqueous binder systems for granular and/orfibrous substrates comprising a polycarboxy polymer having a weightaverage molecular weight of at least 1000 g/mol and a polysaccharidehaving a weight average molecular weight of at least 10 000 g/mol, theamounts of which are determined such that the equivalence ratio ofcarboxyl groups to hydroxyl groups is in the range from 3:1 to 1:20.

EP-A 1 578 879 discloses aqueous binder compositions for coating glassfibers, comprising a polycarboxy polymer, a polyalcohol having at leasttwo hydroxyl groups and also a so-called water-soluble extender, whereinpolysaccharides having an average molecular weight below 10 000 g/molare proposed as water-soluble extender.

WO 2008/150647 discloses aqueous binder systems for production of fibermats, comprising a urea-formaldehyde resin and an aqueous copolymerdispersion whose copolymer is constructed essentially of styrene, alkylacrylates and/or methacrylates, acrylonitrile and an optionallysubstituted acrylamide. Optionally, the aqueous copolymer dispersion mayfurther comprise starch.

US-A 2009/170978 discloses aqueous binder systems for fiber webs,comprising an aqueous copolymer dispersion whose copolymer comprisesbetween 5 and 40 wt % of at least one carboxyl-containing monomer inpolymerized form, and a natural binder component selected from the groupcomprising polysaccharides, vegetable proteins, lignins and/orlignosulfonates.

Prior art binder systems are disadvantageous in that they, in theproduction of shaped articles from granular and/or fibrous substrates,are not always fully satisfactory especially with regard to mechanicalproperties thereof.

The problem addressed by the present invention was therefore that ofproviding aqueous binder compositions whereby the disadvantages of priorart aqueous binder compositions can be overcome and whereby shapedarticles having improved transverse breaking strength at roomtemperature and/or improved heat resistance at elevated temperature canbe made available.

The problem was solved by the aqueous binder composition mentioned atthe beginning.

One essential constituent of the aqueous binder composition is a polymerP which in polymerized form is constructed from

-   ≧0.1 and ≦15 wt % of at least one acid-functional ethylenically    unsaturated monomer and/or at least one α,β-monoethylenically    unsaturated C₃ to C₆ mono- or dicarboxamide (monomers A)-   ≧8.0 and ≦30 wt % of at least one ethylenically unsaturated    carboxylic acid nitrile or dinitrile (monomers B)-   ≧0 and ≦5.0 wt % of at least one crosslinking monomer having two or    more nonconjugated ethylenically unsaturated groups (monomers C)-   ≧0 and ≦10 wt % of at least one monoethylenically unsaturated silane    compound (monomers D)-   ≧20 and ≦70 wt % of at least one ethylenically unsaturated monomer    whose homopolymer has a glass transition temperature ≦30° C.    (monomers E) and which differs from the monomers A to D, and-   ≧25 and ≦71.9 wt % of at least one ethylenically unsaturated monomer    whose homopolymer has a glass transition temperature ≧50° C.    (monomers F) and which differs from the monomers A to D.

As monomers A there come into consideration all ethylenicallyunsaturated compounds which include at least one acid group [protondonor], for example a sulfonic acid, phosphonic acid or carboxylic acidgroup, e.g., vinylsulfonic acid, allylsulfonic acid, styrenesulfonicacid, 2-acrylamidomethylpropanesulfonic acid, vinylphosphonic acid,allylphosphonic acid, styrenephosphonic acid and2-acrylamido-2-methylpropanephosphonic acid. Advantageously, however,the monomers A are α,β-monoethylenically unsaturated, especially C₃ toC₆ and preferably C₃ or C₄ mono- or dicarboxylic acids such as, forexample acrylic acid, methacrylic acid, ethylacrylic acid, itaconicacid, allylacetic acid, crotonic acid, vinylacetic acid, fumaric acid,maleic acid, 2-methylmaleic acid. But the monomers A also comprise theanhydrides of appropriate α,β-monoethylenically unsaturated dicarboxylicacids, for example maleic anhydride or 2-methylmaleic anhydride. Theacid-functional monomer A is preferably selected from the groupcomprising acrylic acid, methacrylic acid, crotonic acid, fumaric acid,maleic acid, maleic anhydride, 2-methylmaleic acid and itaconic acid, ofwhich acrylic acid, methacrylic acid and/or itaconic acid areparticularly preferred. It will be appreciated that the monomers A alsocomprise the fully or partially neutralized water-soluble salts,especially the alkali metal or ammonium salts, of the aforementionedacids.

As monomers A there come into consideration furthermore allα,β-monoethylenically unsaturated C₃ to C₆ mono- or dicarboxamides. Themonomers A likewise include the aforementioned compounds whosecarboxamide group is substituted with an alkyl group or with a methylolgroup. Examples of monomers A are the amides or diamides ofα,β-monoethylenically unsaturated C₃ to C₆ and preferably C₃ or C₄ mono-or dicarboxylic acids such as, for example, acrylamide, methacrylamide,ethylacrylamide, itaconic acid monoamide, itaconic acid diamide,allylacetamide, crotonic acid monoamide, crotonic acid diamide,vinylacetamide, fumaric acid monoamide, fumaric acid diamide, maleicacid monoamide, maleic acid diamide, 2-methylmaleic acid monoamide and2-methylmaleic acid diamide. Examples of α,β-monoethylenicallyunsaturated C₃ to C₆ mono- or dicarboxamides whose carboxamide group aresubstituted with an alkyl group or with a methylol group areN-alkylacrylamides and N-alkylmethacrylamides, e.g.,N-tert-butylacrylamide and N-tert-butylmethacrylamide,N-methylacrylamide and N-methylmethacrylamide, and N-methylolacrylamideand N-methylolmethacrylamide. Preferred amidic monomers A areacrylamide, methacrylamide, N-methylolacrylamide and/orN-methylolmethacrylamide, of which methylolacrylamide and/orN-methylolmethacrylamide are particularly preferred.

Particular preference for use as monomers A is given to acrylic acid,methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleicanhydride, 2-methylmaleic acid, itaconic acid, acrylamide,methacrylamide, N-methylolacrylamide and/or N-methylolmethacrylamide, ofwhich acrylic acid, methacrylic acid, itaconic acid, methylolacrylamideand/or N-methylolmethacrylamide are particularly preferred.

The amount of monomer A polymerized into polymer P is ≧0.1 and ≦15 wt %,preferably ≧0.5 and ≦1.0 wt % and more preferably ≧3.0 and ≦8.5 wt %.

As monomers B there come into consideration all ethylenicallyunsaturated compounds which include at least one nitrile group.Advantageously, however, the monomers B are nitriles derived from theaforementioned α,β-monoethylenically unsaturated, especially C₃ to C₆and preferably C₃ or C₄, mono- or dicarboxylic acids, for exampleacrylonitrile, methacrylonitrile, maleonitrile and/or fumaronitrile, ofwhich acrylonitrile and/or methacrylonitrile are particularly preferred.

The amount of monomer B polymerized into polymer P is ≧8.0 and ≦30 wt %,preferably ≧10 and ≦25 wt % and more preferably ≧10 and ≦20 wt %.

As monomers C there come into consideration all compounds which includeat least two nonconjugated ethylenically unsaturated groups. Examplesthereof are monomers including two vinyl radicals, monomers includingtwo vinylidene radicals and also monomers including two alkenylradicals. Of particular advantage here are the diesters of dihydricalcohols with α,β-monoethylenically unsaturated monocarboxylic acids,among which acrylic acid and methacrylic acid are preferred. Examples ofsuch monomers including two nonconjugated ethylenically unsaturateddouble bonds are alkylene glycol diacrylates and alkylene glycoldimethacrylates, such as ethylene glycol diacrylate, 1,2-propyleneglycol diacrylate, 1,3-propylene glycol diacrylate, 1,3-butylene glycoldiacrylate, 1,4-butylene glycol diacrylate and ethylene glycoldimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3-propyleneglycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butyleneglycol dimethacrylate, triesters of trihydric alcohols withα,β-monoethylenically unsaturated monocarboxylic acids, for exampleglycerol triacrylate, glycerol trimethacrylate, trimethylolpropanetriacrylate, trimethylolpropane trimethacrylate, and alsodivinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate,allyl acrylate, diallyl maleate, diallyl fumarate,methylenebisacrylamide, cyclopentadienyl acrylate, triallyl cyanurate ortriallyl isocyanurate. 1,4-butylene glycol diacrylate, allylmethacrylate and/or divinylbenzene are particularly preferred.

The amount of monomer C polymerized into polymer P is ≧0 and ≦5.0 wt %,preferably ≧0 and ≦3.0 wt % and more preferably ≧0 and ≦1.5 wt %.

As monomers D there come into consideration all monoethylenicallyunsaturated silane compounds. The monomers D comprise a hydrolyzablesilane group with particular advantage. Hydrolyzable silane groupsadvantageously comprise at least one alkoxy group or a halogen atom,such as chlorine for example. Monomers D which can be used withadvantage for the purposes of the present invention are disclosed in WO2008/150647, page 9, line 5 to 25. These monomers D are herebyincorporated herein by reference. It is particularly advantageous to use3-methacryloyloxypropyltrimethoxysilane,3-methacryloyloxypropyltriethoxysilane, vinyltriacetoxysilane and/orvinylethoxydimethoxysilane. The monomers D are preferably used wheneverinorganic granular and/or fibrous substrates, more particularly glassfibers or mineral fiber for example asbestos or rock wool, are to bebonded.

The amount of monomer D optionally polymerized into polymer P is ≧0 and≦10 wt %, preferably ≧0 and ≦5.0 wt % and more preferably 0 wt % in onepreferred embodiment. In another preferred embodiment, especially wheninorganic granular and/or fibrous substrates are to be bonded, theamount of monomer D polymerized into polymer P is ≧0.1 and ≦10 wt %,advantageously ≧0.1 and ≦5.0 wt % and more advantageously ≧0.5 and ≦2.5wt %.

As monomers E there come into consideration all ethylenicallyunsaturated monomers whose homopolymer have a glass transitiontemperature ≦30° C. and which differ from the monomers A to D. Suitablemonomers E are for example conjugated aliphatic C₄ to C₉ dienecompounds, esters of vinyl alcohol and a C₁ to C₁₀ monocarboxylic acid,C₁ to C₁₀ alkyl acrylate, C₅ to C₁₀ alkyl methacrylate, C₅ to C₁₀cycloalkyl acrylate, C₅ to C₁₀ cycloalkyl methacrylate, C₁ to C₁₀dialkyl maleate and/or C₁ to C₁₀ dialkyl fumarate, vinyl ethers of C₃ toC₁₀ alkanols, branched and unbranched C₃ to C₁₀ olefins. It isadvantageous to use such monomers E whose homopolymers have Tg values<0° C. It is particularly advantageous for vinyl acetate, ethylacrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate,sec-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-hexylmethacrylate, 2-ethylhexyl methacrylate, di-n-butyl maleate, di-n-butylfumarate to be used as monomers E, for which 2-ethylhexyl acrylate,n-butyl acrylate, 1,4-butadiene and/or ethyl acrylate are particularlypreferred.

The amount of monomer E polymerized into polymer P is ≧20 and ≦70 wt %,preferably ≧25 and ≦65 wt % and more preferably ≧30 and ≦60 wt %.

As monomers F there come into consideration all ethylenicallyunsaturated monomers whose homopolymer have a glass transitiontemperature ≧50° C. and which differ from the monomers A to D. Suitablemonomers F are for example vinylaromatic monomers and C₁ to C₄ alkylmethacrylates. Vinylaromatic monomers are more particularly derivativesof styrene or of α-methylstyrene in each of which the phenyl nuclei areoptionally substituted by 1, 2 or 3 C₁ to C₄ alkyl groups, halogen,especially bromine or chlorine and/or methoxy groups. Preference isgiven to such monomers whose homopolymers have a glass transitiontemperature ≧80° C. Particularly preferred monomers are styrene,α-methylstyrene, o-vinyltoluene, p-vinyltoluene, p-acetoxystyrene,p-bromostyrene, p-tert-butylstyrene, o-chlorostyrene, m-chlorostyrene,p-chlorostyrene, methyl methacrylate, tert-butyl acrylate, tert-butylmethacrylate, ethylmethacrylate, isobutyl methacrylate, n-hexylacrylate, cyclohexyl methacrylate, but also for example tert-butyl vinylether or cyclohexyl vinyl ether, although methyl methacrylate, styreneand/or tert-butyl methacrylate are particularly preferred.

The amount of monomer F polymerized into polymer P is ≧25 and ≦71.9 wt%, preferably ≧25 and ≦64.5 wt % and more preferably ≧25 and ≦57 wt %.

The reference to a glass transition temperature Tg is to be understoodas meaning the glass transition temperature limit which the glasstransition temperature approaches with increasing molecular weight,according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift für Polymere,volume 190, page 1, equation 1). Tg is determined by the DSC method(Differential Scanning calorimetry, 20 K/min, midpoint measurement, DIN53 765). The Tg values for the homopolymers of most monomers are knownand are listed for example in Ullmann's Encyclopedia of IndustrialChemistry, V C H Weinheim, 1992, Volume 5, Vol. A21, p. 169; furthersources for glass transition temperatures of homopolymers include forexample J. Brandrup, E. H. Immergut, Polymer Handbook, 1st Ed., J.Wiley, New York 1966, 2nd Ed. J. Wiley, New York 1975, and 3rd Ed. J.Wiley, New York 1989).

C₁ to C₁₀ Alkyl groups herein are linear or branched alkyl radicals of 1to 10 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl,tert-pentyl n-hexyl, 2-ethylhexyl, n-nonyl or n-decyl. C₅ to C₁₀cycloalkyl groups are preferably cyclopentyl or cyclohexyl groups, whichmay optionally be substituted by 1, 2 or 3 C₁ to C₄ alkyl groups.

The aqueous binder compositions advantageously comprise polymers P whoseat least one monomer E is selected from the group comprising conjugatedaliphatic C₄ to C₉ diene compounds, esters of vinyl alcohol and a C₁ toC₁₀ monocarboxylic acid, C₁ to C₁₀ alkyl acrylate, C₅ to C₁₀ alkylmethacrylate, C₅ to C₁₀ cycloalkyl acrylate, C₅ to C₁₀ cycloalkylmethacrylate, C₁ to C₁₀ dialkyl maleinate and/or C₁ to C₁₀ dialkylfumarate and at least one monomer F is selected from the groupcomprising vinylaromatic monomers and/or C₁ to C₄ alkyl methacrylate.

It is likewise advantageous for the aqueous binder compositions toinclude polymers P comprising ≧0 and ≦1.5 wt % of at least one monomer Cin polymerized form.

In one preferred embodiment, the aqueous binder composition comprises apolymer P constructed from

-   ≧0.5 and ≦10 wt % of at least one monomer A,-   ≧10 and ≦25 wt % of at least one monomer B,-   ≧0 and ≦1.5 wt % of at least one monomer C,-   ≧0 and ≦5.0 wt % of at least one monomer D,-   ≧25 and ≦65 wt % of at least one monomer E, and-   ≧25 and ≦64.5 wt % of at least one monomer F.

In one preferred embodiment, the aqueous binder composition comprises apolymer P constructed in polymerized form from

-   ≧3.0 and ≦8.5 wt % of acrylic acid, methacrylic acid, itaconic acid,    acrylamide, methacrylamide, N-methylolacrylamide and/or    N-methylolmethacrylamide-   ≧10 and ≦20 wt % of acrylonitrile and/or methacrylonitrile-   ≧0 and ≦1.5 wt % of 1,4-butylene glycol diacrylate, allyl    methacrylate and/or divinylbenzene-   ≧30 and ≦60 wt % of 2-ethylhexyl acrylate, n-butyl acrylate,    1,4-butadiene and/or ethyl acrylate, and-   ≧25 and ≦57 wt % of methyl methacrylate, styrene and/or tert-butyl    methacrylate.

The preparation of polymers P will in principle be familiar to a personskilled in the art and is effected for example through free-radicalpolymerization of monomers A to F by the method of substance, emulsion,solution, precipitation or suspension polymerization, althoughfree-radically initiated aqueous emulsion polymerization is particularlypreferred. It is therefore advantageous according to the presentinvention for the polymer P to be dispersed in an aqueous medium, i.e.,used in the form of an aqueous polymer dispersion.

The performance of free-radically initiated emulsion polymerizations ofethylenically unsaturated monomers in an aqueous medium has beenextensively described and therefore is sufficiently familiar to a personskilled in the art [cf. Emulsion polymerization in Encyclopedia ofPolymer Science and Engineering, Vol. 8, pages 659 ff. (1987); D. C.Blackley, in High Polymer Latices, Vol. 1, pages 35 ff. (1966); H.Warson, The Applications of Synthetic Resin Emulsions, chapter 5, pages246 ff. (1972); D. Diederich, Chemie in unserer Zeit 24, pages 135 to142 (1990); Emulsion Polymerisation, Interscience Publishers, New York(1965); DE-A 40 03 422 and Dispersionen synthetischer Hochpolymerer, F.Hölscher, Springer-Verlag, Berlin (1969)]. A free-radically initiatedaqueous emulsion polymerization is typically carried out by theethylenically unsaturated monomers being dispersed in an aqueous medium,generally by co-use of dispersing assistants, such as emulsifiers and/orprotective colloids, and polymerized using at least one water-solublefree-radical polymerization initiator. Frequently, in the aqueouspolymer dispersions obtained, the residual contents of unconvertedethylenically unsaturated monomers are reduced by chemical and/orphysical methods likewise known to a person skilled in the art [see forexample EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586 and19847115], the polymer solids content is adjusted to a desired value bythinning or concentrating, or the aqueous polymer dispersion is mixedwith further customary addition agents, for example bactericidal, foam-or viscosity-modifying additives. From this general procedure, theproduction of an aqueous dispersion of polymer P merely differs by thespecific use of the aforementioned monomers A to F. It will beappreciated in this connection that producing polymer P herein shallalso comprise the seed, staged and gradient modes of operation which arefamiliar to a person skilled in the art.

Therefore, according to the present invention, the aqueous bindercompositions are advantageously obtained using aqueous dispersions of apolymer P constructed from

-   -   ≧0.1 and ≦15 wt % of at least one monomer A    -   ≧8.0 and ≦30 wt % of at least one monomer B    -   ≧0 and ≦5.0 wt % of at least one monomer C    -   ≧0 and ≦10 wt % of at least one monomer D    -   ≧20 and ≦70 wt % of at least one monomer E, and    -   ≧25 and ≦71.9 wt % of at least one monomer F,        advantageously from

-   ≧0.5 and ≦10 wt % of at least one monomer A,

-   ≧10 and ≦25 wt % of at least one monomer B,

-   ≧0 and ≦1.5 wt % of at least one monomer C,

-   ≧0 and ≦5.0 wt % of at least one monomer D,

-   ≧25 and ≦65 wt % of at least one monomer E, and

-   ≧25 and ≦64.5 wt % of at least one monomer F    and more advantageously from

-   ≧3.0 and ≦8.5 wt % of acrylic acid, methacrylic acid, itaconic acid,    acrylamide, methacrylamide, N-methylolacrylamide and/or    N-methylolmethacrylamide

-   ≧10 and ≦20 wt % of acrylonitrile and/or methacrylonitrile

-   ≧0 and ≦1.5 wt % of 1,4-butylene glycol diacrylate, allyl    methacrylate and/or divinylbenzene

-   ≧30 and ≦60 wt % of 2-ethylhexyl acrylate, n-butyl acrylate,    1,4-butadiene and/or ethyl acrylate, and

-   ≧25 and ≦57 wt % of methyl methacrylate, styrene and/or tert-butyl    methacrylate,    in polymerized form.

The polymers P used according to the present invention are obtainable inthe form of their aqueous polymer dispersion (aqueous polymer Pdispersion) by initially charging the overall amount of monomers A to F(overall amount of monomers) in the aqueous reaction medium beforeinitiating the polymerization reaction. However, it is also possible tooptionally merely initially charge a portion of monomers A to F in theaqueous reaction medium before initiating the polymerization reactionand then, after initiating the polymerization, to add the overall amountor, as may be, the remaining quantity under polymerization conditionsduring the free-radical emulsion polymerization at the rate ofconsumption, continuously with constant or varying flow rates, ordiscontinuously. The monomers A to F can be dosed as separate individualstreams, as homogeneous or inhomogeneous (partial) mixtures, or asmonomer emulsion. Advantageously, the monomers A to F are dosed in theform of a monomer mixture and more particularly in the form of anaqueous monomer emulsion.

The aqueous polymer P dispersion used according to the present inventionis obtained by co-using dispersing assistants which keep both themonomer droplets and the produced polymer particles in a state ofdispersion in the aqueous medium and so ensure the stability of theaqueous polymer dispersion produced. As dispersing assistants there comeinto consideration the protective colloids typically used forperformance of free-radical aqueous emulsion polymerizations as well asemulsifiers.

Suitable protective colloids are for example polyvinyl alcohols,polyalkylene glycols, alkali metal salts of polyacrylic acids andpolymethacrylic acids, gelatin derivatives or acrylic acid, methacrylicacid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and/or4-styrenesulfonic acid-containing copolymers and their alkali metalsalts but also N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole,1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine,acrylamide, methacrylamide, amino-bearing acrylates, methacrylates,acrylamides and/or methacrylamides-containing homo- and copolymers. Anextensive description of further suitable protective colloids is givenin Houben-Weyl, Methoden der organischen Chemie, volume XIV/1,Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, pages 411to 420.

It will be appreciated that mixtures of protective colloids and/oremulsifiers can also be used. Frequently, the dispersing agents used areexclusively emulsifiers whose relative molecular weights are typicallybelow 1000, unlike protective colloids. They can be anionic, cationic ornonionic in nature. It will be appreciated that, when the mixtures ofsurface-active substances are used, the individual components have to becompatible with each or one another, which in the case of doubt can beverified in a few preliminary tests. In general, anionic emulsifiers arecompatible with other anionic emulsifiers and with nonionic emulsifiers.The same applies to cationic emulsifiers, while anionic and cationicemulsifiers are usually not compatible with one another. An overview ofsuitable emulsifiers is given in Houben-Weyl, Methoden der organischenChemie, volume XIV/1, Makromolekulare Stoffe, Georg-Thieme-Verlag,Stuttgart, 1961, pages 192 to 208.

However, especially emulsifiers are used as dispersing assistants.

Customary nonionic emulsifiers are for example ethoxylated mono-, di-and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C₄ to C₁₂) andalso ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: C₈to C₃₆). Examples thereof are the Lutensol® A brands (C₁₂C₁₄ fattyalcohol ethoxylates, EO degree: 3 to 8), Lutensol® AO brands (C₁₃C₁₅ oxoprocess alcohol ethoxylates, EO degree: 3 to 30), Lutensol® AT brands(C₁₆C₁₈ fatty alcohol ethoxylates, EO degree: 11 to 80), Lutensol® ONbrands (C₁₀-oxo process alcohol ethoxylates, EO degree: 3 to 11) and theLutensol® TO brands (C₁₃ oxo process alcohol ethoxylates, EO degree: 3to 20) from BASF SE.

Customary anionic emulsifiers are for example alkali metal and ammoniumsalts of alkyl sulfates (alkyl radical: C₈ to C₁₂), of sulfuricmonoesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical:C₁₂ to C₁₈) and ethoxylated alkylphenols (EO degree: 3 to 50, alkylradical: C₄ to C₁₂), of alkylsulfonic acids (alkyl radical: C₁₂ to C₁₈)and of alkylarylsulfonic acids (alkyl radical: C₉ to C₁₈).

Suitable anionic emulsifiers further include compounds of the generalformula (I)

where R¹ and R² are H atoms or C₄ to C₂₄ alkyl that are not H atoms atthe same time, and M¹ and M² can be alkali metal ions and/or ammoniumions. In the general formula (I), R¹ and R² are preferably linear orbranched alkyl radicals of 6 to 18 carbon atoms and more particularly of6, 12 and 16 carbon atoms, or hydrogen, with the proviso that R¹ and R²are not both an H atom at the same time. M¹ and M² are each preferablysodium, potassium or ammonium, of which sodium is particularlypreferred. Particularly advantageous are compounds (I) in which M¹ andM² are both sodium, R¹ is a branched alkyl radical of 12 carbon atomsand R² an H atom or R¹. Technical grade mixtures are frequently usedthat include a 50 to 90 wt % fraction of monoalkylated product, forexample Dowfax® 2A1 (trademark of Dow Chemical Company). Compounds (I)are common knowledge, for example from U.S. Pat. No. 4,269,749, andcommercially available.

Suitable cation-active emulsifiers are generally C₆-C₁₈-alkyl-,-alkylaryl- or heterocyclyl-containing primary, secondary, tertiary orquaternary ammonium salts, alkanolammonium salts, pyridinium salts,imidazolinium salts, oxazolinium salts, morpholinium salts, thiazoliniumsalts and also salts of amine oxides, quinolinium salts, isoquinoliniumsalts, tropylium salts, sulfonium salts and phosphonium salts. Exampleswhich may be mentioned are dodecylammonium acetate and the correspondingsulfate, the sulfates or acetates of the various2-(N,N,N-trimethylammonium)ethyl paraffinic acid esters,N-cetylpyridinium sulfate, N-laurylpyridinium sulfate and alsoN-cetyl-N,N,N-trimethylammonium sulfate,N-dodecyl-N,N,N-trimethylammonium sulfate,N-octyl-N,N,N-trimethylammonium sulfate,N,N-distearyl-N,N-dimethylammonium sulfate and also the Geminisurfactant N,N′(lauryldimethyl)ethylenediamine disulfate, ethoxylatedtallowalkyl N-methylammonium sulfate and ethoxylated oleylamine (forexample Uniperol® AC from BASF SE, about 11 ethylene oxide units).Numerous further examples are given in H. Stache, Tensid-Taschenbuch,Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's,Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989. It isbeneficial when the anionic counter-groups have very lownucleophilicity, for example perchlorate, sulfate, phosphate, nitrateand carboxylates, for example acetate, trifluoroacetate,trichloroacetate, propionate, oxalate, citrate, benzoate, and alsoconjugated anions of organosulfonic acids, for example methylsulfonate,trifluoromethylsulfonate and para-toluenesulfonate, furthertetrafluoroborate, tetraphenylborate, tetrakis(pentafluorophenyl)borate,tetrakis[bis(3,5-trifluoromethyl)phenyl]borate, hexafluorophosphate,hexafluoroarsenate or hexafluoroantimonate.

The emulsifiers preferred for use as dispersing assistants areadvantageously used in an overall amount≧0.005 and ≦10 wt %, preferably≧0.01 and ≦5 wt % and more particularly ≧0.1 and ≦3 wt %, all based onthe overall amount of monomers A to F (total monomer quantity).

The overall amount of the protective colloids used as dispersingassistants in addition to or in lieu of emulsifiers is often ≧0.1 and≦40 wt % and frequently ≧0.2 and ≦25 wt %, all based on the totalmonomer quantity.

Preferably, however, it is anionic and/or nonionic emulsifiers and morepreferably anionic emulsifiers that are used as dispersing assistants.

The polymer P dispersion used according to the present invention isobtainable by initially charging the overall amount of dispersingassistant in the aqueous reaction medium before initiating thepolymerization reaction. However, it is also possible to optionallymerely initially charge a portion of the dispersing assistant in theaqueous reaction medium before initiating the polymerization reactionand then to add the overall amount or as the case may be any remainingquantity of dispersing assistant under polymerization conditions duringthe free-radical emulsion polymerization, continuously or batchwise.Preferably, the main or overall quantity of dispersing assistant isadded in the form of an aqueous monomer emulsion.

The free-radically initiated aqueous emulsion polymerization istriggered using a free-radical polymerization initiator. In principle,not only peroxides but also azo compounds can be concerned here. Redoxinitiator systems also come into consideration, as will be appreciated.As peroxides there can be used in principle inorganic peroxides, such ashydrogen peroxide or peroxodisulfates, such as the mono- or di-alkalimetal or ammonium salts of peroxodisulfuric acid, for example its mono-and di-sodium, potassium or ammonium salts or organic peroxides, such asalkyl hydroperoxides, for example tert-butyl hydroperoxide, p-mentylhydroperoxide or cumyl hydroperoxide, and also dialkyl or diarylperoxides, such as di-tert-butyl or dicumyl peroxide. As azo compound itis essentially 2,2′-azobis(isobutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile) and 2,2′-azobis(amidinopropyl)dihydrochloride (AIBA, corresponds to V-50 from Wako Chemicals) whichare used. As oxidizing agents for redox initiator systems it isessentially the abovementioned peroxides which come into consideration.As corresponding reducing agents there can be used sulfur compounds oflow oxidation state, such as alkali metal sulfites, for examplepotassium and/or sodium sulfite, alkali metal hydrogensulfites, forexample potassium and/or sodium hydrogensulfite, alkali metalmetabisulfites, for example potassium and/or sodium metabisulfite,formaldehydesulfoxylates, for example potassium and/or sodiumformaldehydesulfoxylate, alkali metal salts, specifically potassiumand/or sodium salts of aliphatic sulfinic acids and alkali metalhydrogensulfides, for example potassium and/or sodium hydrogensulfide,salts of multivalent metals, such as iron(II) sulfate, iron(II) ammoniumsulfate, iron(II) phosphate, enediols, such as dihydroxymaleic acid,benzoin and/or ascorbic acid and also reducing saccharides, such assorbose, glucose, fructose and/or dihydroxyacetone. In general, theamount of free-radical initiator used is from 0.01 to 5 wt %, preferably0.1 to 3 wt % and more preferably 0.2 to 1.5 wt %, based on the totalmonomer quantity.

The polymer P dispersion used according to the present invention isobtainable by initially charging the overall amount of free-radicalinitiator in the aqueous reaction medium before initiating thepolymerization reaction. However, it is also possible to optionallyinitially charge merely a portion of the free-radical initiator in theaqueous reaction medium before initiating the polymerization reactionand then to add the overall amount or as the case may be any remainingquantity under polymerization conditions during the free-radicalemulsion polymerization at the rate of consumption, continuously ordiscontinuously.

Initiating the polymerization reaction refers to starting thepolymerization reaction of the monomers in the polymerization vesselafter free-radical formation on the part of the free-radical initiator.The polymerization reaction can be initiated by addition of free-radicalinitiator to the aqueous polymerization mixture in the polymerizationvessel under polymerization conditions. However, it is also possible forthe addition of some or all of the free-radical initiator to the aqueouspolymerization mixture comprising the initially charged monomers, in thepolymerization vessel, to take place under conditions which are notsuitable for triggering a polymerization reaction, for example at lowtemperature, and for polymerization conditions to be established in theaqueous polymerization mixture thereafter. Polymerization conditions aregenerally those temperatures and pressures under which thefree-radically initiated aqueous emulsion polymerization proceeds at asufficient polymerization rate. They are more particularly dependent onthe free-radical initiator used. Advantageously, free-radical initiatortype and quantity, the polymerization temperature and the polymerizationpressure are selected such that the free-radical initiator has ahalf-life <3 hours, more advantageously <1 hour and even moreadvantageously <30 minutes, while sufficient starting free-radicals areavailable at all times in order that the polymerization reaction may beinitiated and maintained.

The entire range from 0 to 170° C. comes into consideration as reactiontemperature for the free-radical aqueous emulsion polymerization.Temperatures employed are generally in the range from 50 to 120° C.,preferably in the range from 60 to 110° C. and more preferably in therange from 70 to 100° C. The free-radical aqueous emulsionpolymerization can be carried out at a pressure below, equal to or above1 atm [1.013 bar (absolute), atmospheric pressure], so that thepolymerization temperature can exceed 100° C. and range up to 170° C. Inthe presence of monomers A to F having a low boiling point, the emulsionpolymerization is preferably performed under elevated pressure. Thispressure can assume values of 1.2, 1.5, 2, 5, 10, 15 bar (absolute) oreven higher. When the emulsion polymerization is carried out underreduced pressure, pressures of 950 mbar, frequently of 900 mbar andoften 850 mbar (absolute) are set. Advantageously, the free-radicalaqueous emulsion polymerization is carried out at 1 atm in the absenceof oxygen, more particularly under an inert gas, for example undernitrogen or argon.

The aqueous reaction medium can in principle also comprise minor amounts(≦5 wt %) of water-soluble organic solvents, for example methanol,ethanol, isopropanol, butanols, pentanols, but also acetone etc.Preferably, however, the process of the present invention is carried outin the absence of such solvents.

In addition to the aforementioned components, chain transfer agents canoptionally also be used during the emulsion polymerization toreduce/police the molecular weight of the polymers P obtainable by thepolymerization. Here it is essentially aliphatic and/or araliphatichalogen compounds, for example n-butyl chloride, n-butyl bromide,n-butyl iodide, methylene chloride, ethylene dichloride, chloroform,bromoform, bromotrichloromethane, dibromodichloromethane, carbontetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide,organic thio compounds, such as primary, secondary or tertiary aliphaticthiols, for example ethanethiol, n-propanethiol, 2-propanethiol,n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pentanethiol,2-pentanethiol, 3-pentanethiol, 2-methyl-2-butanethiol,3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexanethiol,2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol,4-methyl-2-pentanethiol, 2-methyl-3-pentanethiol,3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol,n-heptanethiol and its isomeric compounds, n-octanethiol and itsisomeric compounds, n-nonanethiol and its isomeric compounds,n-decanethiol and its isomeric compounds, n-undecanethiol and itsisomeric compounds, n-dodecanethiol and its isomeric compounds,n-tridecanethiol and its isomeric compounds, substituted thiols, forexample 2-hydroxyethanethiol, aromatic thiols, such as benzenethiol,ortho-benzenethiol, meta-methylbenzenethiol or para-methylbenzenethiol,and also all further sulfur compounds described in Polymerhandbook 3rdedition, 1989, J. Brandrup and E. H. Immergut, John Wiley & Sons,section II, pages 133 to 141, but also aliphatic and/or aromaticaldehydes, such as acetaldehyde, propionaldehyde and/or benzaldehyde,unsaturated fatty acids, such as oleic acid, dienes with nonconjugateddouble bonds, such as divinylmethane or vinylcyclohexane or hydrocarbonshaving readily extractable hydrogen atoms, such as toluene for example,which are used. But it is also possible to use mixtures ofaforementioned chain transfer agents that are noninterfering.

The total amount of chain transfer agents optionally used during theemulsion polymerization is generally ≦5 wt %, often ≦3 wt % andfrequently ≦1 wt %, based on the total monomer quantity.

It is beneficial when all or some of the optional chain transfer agentis added to the aqueous reaction medium prior to initiating thefree-radical polymerization. In addition, all or some of the chaintransfer agent can advantageously be added to the aqueous reactionmedium together with the monomers A to F during the polymerization.

The polymers P used according to the present invention can in principlehave glass transition temperatures Tg in the range of ≧−70 and ≦150° C.Advantageously, the monomers A, B, D, E and F are chosen in terms oftype and amount such that the polymers formed merely therefrom have aglass transition temperature Tg in the range of ≧−10 and ≦70° C. andadvantageously in the range ≧5 and ≦50° C. and more advantageously inthe range ≧15 and ≦45° C. Glass transition temperature Tg herein is tounderstood as meaning the midpoint temperature as per ASTM D 3418-82,determined by differential scanning calorimetry (DSC) [cf. alsoUllmann's Encyclopedia of Industrial Chemistry, page 169, Verlag Chemie,Weinheim, 1992 and Zosel in Farbe and Lack, 82, pages 125 to 134, 1976].

According to Fox (T. G. Fox, Bull. Am. Phys. Soc. 1956 [Ser. II] 1, page123 and as per Ullmann's Encyclopädie der technischen Chemie, volume 19,page 18, 4th edition, Verlag Chemie, Weinheim, 1980) the glasstransition temperature of at most lightly crosslinked copolymers isgiven to good approximation by:1/Tg=x1/Tg1+x2/Tg2+ . . . xn/Tgn,where x1, x2, xn are the mass fractions of monomers 1, 2, . . . n andTg1, Tg2, Tgn are the glass transition temperatures in degrees kelvin ofthe polymers each constructed of just one of the monomers 1, 2, . . . n.The glass transition temperatures of these homopolymers of mostethylenically unsaturated monomers are known (or are simple to determineexperimentally in a conventional manner) and are listed for example inJ. Brandrup, E. H. Immergut, Polymer Handbook 1st Ed. J. Wiley, NewYork, 1966, 2nd Ed. J. Wiley, New York, 1975 and 3rd Ed. J. Wiley, NewYork, 1989, and also in Ullmann's Encyclopedia of Industrial Chemistry,page 169, Verlag Chemie, Weinheim, 1992.

It is essential that the free-radically initiated aqueous emulsionpolymerization can also be carried out in the presence of a polymerseed, for example in the presence of 0.01 to 3 wt %, frequently of 0.02to 2 wt % and often of 0.04 to 1.5 wt % of a polymer seed, all based onthe total monomer quantity.

A polymer seed is used in particular when the particle size of thepolymer particles to be obtained by free-radical aqueous emulsionpolymerization is to be set to a specific value (see for example U.S.Pat. No. 2,520,959 and U.S. Pat. No. 3,397,165).

One polymer seed used in particular has polymer seed particles with anarrow particle size distribution and weight average diameter Dw≦100 nm,often ≧5 nm to ≦50 nm and often ≧15 nm to ≦35 nm. Weight averageparticle diameter determination is known to a person skilled in the artand is done via the analytical ultracentrifuge method for example.Weight average particle diameter herein is to be understood as being theweight average Dw50 value determined by the analytical ultracentrifugemethod (cf. S. E. Harding et al., Analytical Ultracentrifugation inBiochemistry and Polymer Science, Royal Society of Chemistry, Cambridge,Great Britain 1992, Chapter 10, Analysis of Polymer Dispersions with anEight-Cell-AUC-Multiplexer: High Resolution Particle Size Distributionand Density Gradient Techniques, W. Mächtle, pages 147 to 175).

Narrow particle size distribution herein is to be understood as meaningthat the ratio of the analytical ultracentrifuge method weight averageparticle diameters Dw50 and number average particle diameters DN50[Dw50/DN50] is <2.0, preferably <1.5 and more preferably <1.2 or <1.1.

The polymer seed is typically used in the form of an aqueous polymerdispersion. The aforementioned amount recitations are based on thepolymer solids content of the aqueous polymer seed dispersion.

When a polymer seed is used it is advantageous to employ an exogenouspolymer seed. Unlike an in situ polymer seed, which is prepared in thereaction vessel before the actual emulsion polymerization is commenced,and which generally has the same monomeric composition as the polymerprepared by the ensuing free-radically initiated aqueous emulsionpolymerization, an exogenous polymer seed is a polymer seed which hasbeen prepared in a separate reaction step and whose monomericcomposition differs from the polymer prepared by the free-radicallyinitiated aqueous emulsion polymerization, although this means nothingmore than that different monomers, or monomer mixtures with a differentcomposition, are used for preparing the exogenous polymer seed and forpreparing the aqueous polymer dispersion. Preparing an exogenous polymerseed is familiar to a person skilled in the art and is typicallyaccomplished by the introduction as initial charge to a reaction vesselof a relatively small amount of monomers and also a relatively largeamount of emulsifiers, and by the addition at reaction temperature of asufficient amount of polymerization initiator.

It is preferred in accordance with the present invention to use anexogenous polymer seed having a glass transition temperature ≧50° C.,frequently ≧60° C. or ≧70° C. and often ≧80° C. or ≧90° C. A polystyreneor polymethyl methacrylate polymer seed is preferred in particular.

The total amount of exogenous polymer seed can be initially charged tothe polymerization vessel. But it is also possible to merely include aportion of the exogenous polymer seed in the initial charge to thepolymerization vessel and to add the remainder during the polymerizationtogether with monomers A to F. If necessary, however, the total polymerseed quantity can also be added during the polymerization. Preferably,the total amount of exogenous polymer seed is initially charged to thepolymerization vessel before initiating the polymerization reaction.

The aqueous polymer P dispersions obtainable by emulsion polymerizationtypically have a polymer solids content of ≧10 and ≦70 wt %, frequently≧20 and ≦65 wt % and often ≧25 and ≦60 wt %, all based on the aqueouspolymer dispersion. The number average particle diameter as determinedby quasi-elastic light scattering (ISO standard 13 321) (cumulantz-average) is generally in the range ≧10 and ≦2000 nm, frequently in therange ≧10 and ≦700 nm and often in the range ≧50 to ≦400 nm.

It will be appreciated that aqueous polymer P dispersions are alsoobtainable in principle in the form of so-called secondary polymerdispersions (concerning in-principle preparation of secondary polymerdispersions see for example Eckersley et al., Am. Chem. Soc., Div.Polymer Chemistry, 1977, 38(2), pages 630, 631, U.S. Pat. No. 3,360,599,U.S. Pat. No. 3,238,173, U.S. Pat. No. 3,726,824, U.S. Pat. No.3,734,686 or U.S. Pat. No. 6,207,756). Secondary aqueous polymer Pdispersions are generally obtained when polymers P obtained by themethod of substance or solution polymerization are dissolved in asuitable organic solvent and dispersed in an aqueous medium to formaqueous polymer/solvent (mini)emulsions. Subsequent solvent removalyields the corresponding aqueous polymer P dispersions.

Accordingly, the aqueous binder compositions of the present inventioncomprise aqueous dispersions of polymers P whose number average particlediameter is in the range ≧10 and ≦2000 nm, advantageously in the range≧10 and ≦700 nm and more advantageously in the range ≧50 to ≦400 nm.

At least one saccharide compound S is an essential constituent of theaqueous binder composition as well as at least one polymer P.

A saccharide compound S herein is to be understood as meaningmonosaccharides, oligosaccharides, polysaccharides, sugar alcohols andalso substitution products and derivatives thereof.

Monosaccharides are organic compounds of the generic formulaC_(n)H_(2n)O_(n), where n is an integer 5, 6, 7, 8 or 9. Thesemonosaccharides are also known as pentoses, hexoses, heptoses, octosesor nonoses, and these compounds can be subdivided into the correspondingaldoses, which include an aldehyde group, and ketoses, which include aketo group. Accordingly, monosaccharides comprise aldo- or ketopentoses,aldo- or ketohexoses, aldo- or ketoheptoses, aldo- or ketooctoses oraldo- or ketononoses. Monosaccharide compounds which are preferredaccording to the present invention are the pentoses and hexoses whichalso occur in nature, of which glucose, mannose, galactose and/or xyloseare particularly preferred. It will be appreciated that the presentinvention also comprehends all stereoisomers of all aforementionedmonosaccharides.

Sugar alcohols are the hydrogenation products of the aforementionedaldo- or ketopentoses, aldo- or ketohexoses, aldo- or ketoheptoses,aldo- or ketooctoses or aldo- or ketononoses, which have the generalformula C_(n)H_(2n+2)O_(n), where n is an integer 5, 6, 7, 8 or 9.Mannitol, lactitol, sorbitol and xylitol are preferred sugar alcohols.It will be appreciated that the present invention shall also comprehendall stereoisomers of all aforementioned sugar alcohols.

It is known that the aforementioned monosaccharides are present in theform of their hemiacetals or -ketals, formed from a hydroxyl group andthe aldehyde or keto group, respectively, generally with the formationof a five- or six-membered ring. If, then, a hydroxyl group (from thehemiacetal or hemiketal group or from the carbon scaffold chain) of onemonosaccharide molecule reacts with the hemiacetal or hemiketal group ofanother monosaccharide molecule by water elimination to form an acetalor, respectively, ketal group (such a bond is also called glycosidicbond), disaccharides are obtained (with the general empirical formulaC_(n)H_(2n-2)O_(n-1)). Furthermore, such a disaccharide can react with afurther monosaccharide by water elimination to form a trisaccharide.Further reactions with monosaccharides give tetrasaccharides,pentasaccharides, hexasaccharides, heptasaccharides, octasaccharides,nonasaccharides or decasaccharides. Compounds constructed of at leasttwo but not more than ten monosaccharide structural units via glycosidicbonds are known as oligosaccharides. Preferred oligosaccharides aredisaccharides, among which it is lactose, maltose and/or sucrose whichare particularly preferred. It will be appreciated that the presentinvention shall also comprehend all stereoisomers of all aforementionedoligosaccharides.

Saccharide compounds constructed of more than ten monosaccharidestructural units are herein known as polysaccharide compounds.Polysaccharide compounds can in effect be constructed of the structuralelements of a monosaccharide (so-called homoglycans) or the structuralelements of two or more different monosaccharides (so-calledheteroglycans). It is homoglycans which are preferably used according tothe present invention.

Among the homoglycans it is the starches, which are constructed ofα-D-glucose units, which are particularly preferred. The starchesconsist of the polysaccharides amylose (D-glucose units linked togetherα-1,4-glycosidically and amylopectin (D-glucose units linked togetherα-1,4- and additionally about 4% α-1,6-glycosidically). Naturallyoccurring starch typically comprises about 20 to 30 wt % of amylose andabout 70 to 80 wt % of amylopectin. However, the ratio between amyloseand amylopectin can vary as a result of breeding and according to plantspecies. Useful starches include all native starches, for examplestarches from maize, wheat, oats, barley, rice, millet, potatoes, peas,tapioca, sorghum or sago. Also of interest are those natural starchesthat have a high amount of amylopectin content such as waxy maize starchand waxy potato starch. The amylopectin content of these starches is ≧90wt %, often ≧95 and ≦100 wt %.

It will be appreciated that the term saccharide compound S alsocomprises the substitution products and derivatives of theaforementioned mono-, oligo- and polysaccharide compounds and also ofsugar alcohols.

In substitution products of a saccharide compound S, at least onehydroxyl group of saccharide compound S was functionalized, for exampleby esterification, etherification, oxidation, etc., with preservation ofthe saccharide structure. Esterification for example is effected byreacting the saccharide compound S with organic or inorganic acids,their anhydrides or halides. Phosphated and acetylated saccharidecompounds are of particular interest. Etherification is generallyeffected by reacting the saccharide compounds with organic halogencompounds, epoxides or sulfates in aqueous alkaline solution. Knownethers are alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers andallyl ethers. Oxidation of at least one hydroxyl group using anoxidizing agent customary in the organic chemistry of carbohydrates, forexample nitric acid, hydrogen peroxide, ammonium persulfate,peroxyacetic acid, sodium hypochlorite and/or2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), gives rise to thecorresponding keto compound (on oxidation of a secondary hydroxylgroup), or carboxyl compound (on oxidation of a primary hydroxyl group).

Derivatives of saccharide compounds S are such reaction products ofoligo- and polysaccharides as are obtained by cleaving at least oneacetal or ketal group (at least one glycosidic bond) and therefore bydegrading the original saccharide structure. Such degradation reactionsare familiar to a person skilled in the art and they take place inparticular in that an oligo- or polysaccharide compound is exposed tothermal, enzymatic, oxidative and/or hydrolytic conditions.

By way of saccharide compound S it is advantageous to use starch,cellulose, guaran, xanthan, alginate, pectin, chitosan, gum arabic,carrageenan, agar and/or gellan and also substitution products orderivatives thereof.

Particular preference is given to starches and/or starch derivatives andsubstitution products thereof, advantageously maltodextrin and/orglucose syrup.

DE value is a very common way in commercial practice to characterize thedegree of starch degradation. DE is for dextrose equivalent and refersto the percentage fraction of the dry substance which is attributable toreducing sugars. The DE value therefore corresponds to the amount, ingrams, of glucose (=dextrose) which would have the same reducing powerper 100 g of dry substance. The DE value is a measure of how far polymerdegradation has gone. Hence starches of low DE value have a highproportion of polysaccharides and a low content of low molecular weightmono- and oligosaccharides, while starches of high DE consist in themain of low molecular weight mono- or disaccharides. The maltodextrinspreferred in the context of the present invention have DE values in therange from 3 to 20 and weight average molecular weights in the rangefrom 15000 to 30000 g/mol. A glucose syrup likewise preferred in thecontext of the present invention has DE values in the range from 20 to30 and weight average molecular weights in the range from 3000 to 9000g/mol. Owing to their method of making, these products are obtained inthe form of aqueous solutions and they are therefore generally alsocommercialized as such. Suitable solutions of maltodextrins have solidscontents of 50 to 70 wt %, while suitable solutions of glucose syruphave solids contents of 70 to 95 wt %. Especially maltodextrins,however, are also obtainable in spray-dried form as powders. Preferenceaccording to the present invention is also given to modified degradedstarches which have DE values of 1 to 3 and weight average molecularweights Mw in the range from 100000 to 1000000 g/mol and are typicallyobtainable as a solid material.

The saccharide compound S generally has a weight average molecularweight in the range ≧1000 and ≦5000000 g/mol, preferably in the range≧10000 and ≦3000000 g/mol and more preferably in the range ≧50000 and≦1000000 g/mol. The weight average molecular weight here is determinedusing gel permeation chromatography with defined standards which isfamiliar to a person skilled in the art.

It is preferable when the saccharide compound S used according to thepresent invention has a solubility of ≧10 g, advantageously ≧50 g andmore advantageously ≧100 g per liter of deionized water at 20° C. andatmospheric pressure. The present invention, however, also comprehendsembodiments where the saccharide compound S has a solubility <10 g perliter of deionized water at 20° C. and atmospheric pressure. Dependingon the amount of these employed saccharide compounds S, these can thenalso be present in the form of their aqueous suspension. When saccharidecompounds S are used according to the present invention in terms of typeand amount such that they are present in aqueous suspension, it isadvantageous when the saccharide S particles suspended in the aqueousmedium have an average particle diameters are ≦5 μm, preferably ≦3 μmand more preferably ≦1 μm. Average particle diameters are determined asfor the aqueous polymer P dispersions via the method of quasi-elasticlight scattering (ISO standard 13 321).

It is essential for the present invention that the total amount ofsaccharide compound S can be added to the aqueous polymerization mediumbefore or during the emulsion polymerization of monomers A to F or tothe aqueous dispersion of polymer P on completing the emulsionpolymerization. As will be appreciated, it is also possible to addmerely a portion of saccharide compound S to the aqueous polymerizationmedium before or during the emulsion polymerization of monomers A to Fand the remainder to the aqueous dispersion of polymer P on completingthe emulsion polymerization. When all or some of saccharide compound Sis added before or during the emulsion polymerization of monomers A toF, the quantity added can generally perform the protective colloidfunction, making it possible to reduce the amount of other protectivecolloids and/or emulsifiers and/or optionally to dispense with thementirely.

According to the present invention, the amount of saccharide compound Swill generally be ≧10 and ≦400 parts by weight, advantageously ≧25 and≦300 parts by weight and more advantageously ≧40 and ≦250 parts byweight of saccharide compounds S per 100 parts by weight of polymer P.

It is essential that the aqueous binder composition of the presentinvention, in addition to polymer P and saccharide compound S, mayadditionally comprise still further components familiar to a personskilled in the art in terms of type and quantity, examples beingthickeners, pigment dispersers, dispersants, emulsifiers, buffers,neutralizers, biocides, defoamers, polyol compounds having at least 2hydroxyl groups and having a molecular weight≦200 g/mol, film formationauxiliaries, organic solvents, pigments or fillers etc.

Advantageously, however, the aqueous binder composition comprises ≦1 wt%, more advantageously ≦0.5 wt % of a polyol compound having at least 2hydroxyl groups and having a molecular weight≦200 g/mol, especially ≦150g/mol, for example ethylene glycol, 1,2-propanediol, 1,3-propanediol,1,2,3-propanetriol, 1,2-butanediol, 1,4-butanediol,1,2,3,4-butanetetrol, diethanolamine, triethanolamine, etc., based onthe summed overall amounts of polymer P and saccharide compound S.

It is essential for the present invention that the total amount ofadditional formaldehyde-containing binder components in the aqueousbinder composition is ≦50 parts by weight and advantageously ≦10 partsby weight per 100 parts by weight of the summed overall amounts ofpolymer P and saccharide compound S. It is particularly advantageous forthe binder composition of the present invention to comprise noformaldehyde-containing binder components whatsoever.

For the purposes of this document, formaldehyde-containing bindercomponents are to be understood as meaning binder components preparedusing formaldehyde. Frequently, such formaldehyde-containing bindercomponents are prepared by condensation reaction of a reactant withformaldehyde. The issue with these formaldehyde-containing bindercomponents is that they additionally comprise up to 20000 ppm ofunconverted formaldehyde and, what is more, may additionally releasebonded formaldehyde in the course of the thermal treatment during thecuring operation at a temperature ≦250° C. Examples of such compoundsare the urea-formaldehyde resins, melamine-formaldehyde resins,phenol-formaldehyde resins, guanamine-formaldehyde resins,benzoguanamine-formaldehyde resins or acetoguanamine-formaldehyde resinsthat are familiar to a person skilled in the art.

The aqueous binder composition of the present invention isadvantageously suitable for use as binder for granular and/or fibroussubstrates. Therefore, the aqueous binder compositions mentioned can beused with advantage in the production of shaped articles from granularand/or fibrous substrates.

Granular and/or fibrous substrates are familiar to a person skilled inthe art. They are for example wood chips, wood fibers, cellulose fibers,textile fibers, polymeric fibers, glass fibers, mineral fibers ornatural fibers such as jute, flax, hemp or sisal, but also cork chips orsand and also other organic or inorganic natural and/or syntheticgranular and/or fibrous compounds whose longest dimension is ≦10 mm,preferably ≦5 mm and especially ≦2 mm in the case of granularsubstrates. As will be appreciated, the term substrate shall alsocomprehend the webs obtainable from fibers, for example so-calledmechanically consolidated, for example needled or chemically prebondedfiber webs. It is especially advantageous that the aqueous bindercomposition of the present invention is useful as formaldehyde-freebinder system for the aforementioned fibers and mechanicallyconsolidated or chemically prebonded fiber webs.

The process for producing a shaped article from a granular and/orfibrous substrate and the aforementioned aqueous binder compositionadvantageously comprises applying the aqueous binder composition of thepresent invention to a granular and/or fibrous substrate (byimpregnation), optionally shaping the granular and/or fibrous substratetreated (impregnated) with the aqueous binder composition and thensubjecting the resulting granular and/or fibrous substrate to a thermaltreatment step at a temperature ≧110° C., advantageously ≧130° C. andmore advantageously ≧150° C., wherein the binder composition undergoesfilming and curing.

It is essential that the essential components of the aqueous bindercomposition, i.e., the aqueous dispersion of polymer P and thesaccharide compound S, especially in the form of its solution orsuspension, can be mixed homogeneously before the applying to thegranular and/or fibrous substrate. But it is also possible to mix thesetwo components only immediately before the applying, for example using astatic and/or dynamic mixing device. It is self-evidently also possiblefirst to apply the aqueous dispersion of polymer P and then the aqueoussolution or suspension of saccharide compound S to the granular and/orfibrous substrate, in which case the mixing takes place on the granularand/or fibrous substrate. Similarly, however, it is also possible firstto apply the aqueous solution or suspension of the saccharide compound Sand then the aqueous dispersion of polymer P to the granular and/orfibrous substrate. It will be appreciated that hybrid forms of applyingthe two essential components should also be comprehended according tothe present invention.

Impregnating the granular and/or fibrous substrate generally takes theform of the aqueous binder composition being applied uniformly to thesurface of the fibrous and/or granular substrate. The amount of aqueousbinder composition is chosen such that, per 100 g of granular and/orfibrous substrate, ≧1 g and ≦100 g, preferably ≧2 g and ≦50 g and morepreferably ≧5 g and ≦30 g of binder (reckoned as summed overall amountsof polymer P and saccharide compound S on solids basis) are used. Theactual method of impregnating the granular and/or fibrous substrate isfamiliar to a person skilled in the art and is for example effected bydrenching or spraying the granular and/or fibrous substrate with theaqueous binder composition according to the present invention.

After impregnation, the granular and/or fibrous substrate is optionallyformed into the desired shape, for example by introduction into aheatable press or mold. Thereafter, the shaped impregnated granularand/or fibrous substrate is dried and cured in a manner familiar to aperson skilled in the art.

Drying and/or curing of the optionally shaped impregnated granularand/or fibrous substrate frequently takes place in two temperaturestages, with a drying stage being carried out at a temperature <100° C.,preferably ≧20° C. and ≦90° C. and more preferably ≧40 and ≦80° C. andthe curing stage at a temperature ≧110° C., preferably ≧130 and ≦250° C.and more preferably ≧180° C. and ≦220° C.

However, it is self-evidently also possible for the drying stage and thecuring stage of the shaped articles to take place in one operation, forexample in a molding press.

The shaped articles obtainable by the process of the present inventionhave advantageous properties, more particularly an improved breakingstrength in transverse direction and also improved heat resistance.

The aqueous binder compositions of the present invention are thereforeparticularly advantageous for production of fiber webs based onpolyester and/or glass fiber, which in turn are particularly useful forproduction of bituminized roofing membranes.

The actual method of producing bituminized roofing membranes is familiarto a person skilled in the art and is more particularly effected byapplication of liquefied optionally modified bitumen to one and/or bothof the sides of a polyester and/or glass fiber web bonded with a bindercomposition of the present invention.

The examples which follow illustrate the invention and are nonlimiting.

EXAMPLES A) Preparation of Polymers P as their Aqueous Dispersions

Comparative Polymer Dispersion V1

In a 2 l glass flask fitted with a stirrer and 4 metering devices, 200 gof deionized water and 7.7 g of a 33 wt % aqueous polystyrene seeddispersion (average particle diameter 32 nm) were initially charged at20 to 25° C. (room temperature) and under nitrogen and heated to 85° C.under agitation. After reaching this temperature, 13.8 g of feed 2 weremetered in over 5 minutes. This was followed by the metered addition,commencing at the same time, of feed 1 and the remainder of feed 2 overa period of 3 hours, at continuously constant flow rates and withstirring and while maintaining the aforementioned temperature.

-   Feed 1: aqueous emulsion of-   17.0 g of acrylic acid-   8.5 g of allyl methacrylate-   331 g of styrene-   417 g of n-butyl acrylate-   51.0 g of acrylonitrile-   72.9 g of a 35 wt % aqueous solution of N-methylolacrylamide-   113 g of a 15 wt % aqueous solution of sodium lauryl sulfate    (Disponil® SDS from Cognis GmbH)-   355 g of deionized water-   Feed 2: aqueous solution of-   64.0 g of deionized water-   5.0 g of sodium persulfate

The polymerization mixture was subsequently allowed to undergo secondarypolymerization at 85° C. for 2 hours and cooled down to roomtemperature. A pH value of 7.0 was set by addition of 25 wt % aqueousammonia solution. The aqueous polymer dispersion obtained had a solidscontent of 52.5 wt % based on the total weight of the aqueousdispersion. The number average particle diameter was determined as 242nm.

Solids contents were generally determined by drying a defined amount ofthe aqueous polymer dispersion (about 0.8 g) using the HR73 moisturedeterminator from Mettler Toledo at a temperature of 130° C. to constantweight (about 2 hours). Two measurements were carried out in each case.The value reported in each case is the average value of thesemeasurements.

Number average particle diameters for the polymer particles weregenerally determined by dynamic light scattering on a 0.005 to 0.01weight percent aqueous polymer dispersion at 23° C. using an AutosizerIIC from Malvern Instruments, England. The reported value is the(cumulant z average) of the measured autocorrelation function (ISOstandard 13321).

Comparative Polymer Dispersion V2

The preparation of comparative polymer dispersion V1 was repeated exceptthat feed 1 used 289 g instead of 51.0 g of acrylonitrile, 298 g insteadof 417 g of n-butyl acrylate and 212 g instead of 331 g of styrene.

The aqueous polymer dispersion obtained had a solids content of 52.5% byweight based on the total weight of the aqueous dispersion. The numberaverage particle diameter was determined as 235 nm.

Inventive Polymer Dispersion K1

The preparation of comparative polymer dispersion V1 was repeated exceptthat feed 1 used 85.0 g instead of 51.0 g of acrylonitrile, 399 ginstead of 417 g of n-butyl acrylate and 315 g instead of 331 g ofstyrene.

The aqueous polymer dispersion obtained had a solids content of 53.2% byweight based on the total weight of the aqueous dispersion. The numberaverage particle diameter was determined as 233 nm.

Inventive Polymer Dispersion K2

The preparation of comparative polymer dispersion V1 was repeated exceptthat feed 1 used 136 g instead of 51.0 g of acrylonitrile, 374 g insteadof 417 g of n-butyl acrylate, 289 g instead of 331 g of styrene.

The aqueous polymer dispersion obtained had a solids content of 52.9 wt% based on the total weight of the aqueous dispersion. The numberaverage particle diameter was determined as 237 nm.

Inventive Polymer Dispersion K3

The preparation of comparative polymer dispersion V1 was repeated exceptthat feed 1 used 187 g instead of 51.0 g of acrylonitrile, 348 g insteadof 417 g of n-butyl acrylate and 264 g instead of 331 g of styrene.

The aqueous polymer dispersion obtained had a solids content of 52.7% byweight based on the total weight of the aqueous dispersion. The numberaverage particle diameter was determined as 234 nm.

Inventive Polymer Dispersion K4

The preparation of comparative polymer dispersion V1 was repeated exceptthat feed 1 used 238 g instead of 51.0 g of acrylonitrile, 323 g ofinstead of 417 g of n-butyl acrylate and 238 g instead of 331 g ofstyrene.

The aqueous polymer dispersion obtained had a solids content of 52.9% byweight based on the total weight of the aqueous dispersion. The numberaverage particle diameter was determined as 240 nm.

B) Performance Testing

Production of Impregnating Liquors

Impregnating liquors were produced using Emsol® K55 hydroxypropylatedpotato starch from Emsland Stärke GmbH as a 20 wt % aqueous solution.

The impregnating liquors were produced by the aqueous polymerdispersions K1 to K4 and also the comparative polymer dispersions V1 andV2 being homogeneously mixed with the aqueous solution of Emsol® K55hydroxylated potato starch such that the weight ratio of the particularsolids contents of the aqueous polymer dispersions to the hydroxylatedpotato starch was 7:3 (corresponding to 42.9 parts by weight of starchper 100 parts by weight of solids of the aqueous polymer dispersions).The homogeneous polymer/starch mixtures thus obtained were subsequentlyadjusted to a solids content of 15% by weight by diluting with deionizedwater. The corresponding aqueous dispersions obtained are signified asimpregnating liquors FK1 to FK4 and also FV1 and FV2.

Production of Bonded Fiber Webs

Bonded fiber webs were produced using as raw web a needled polyethyleneterephthalate spunbonded (40 cm length, 37 cm width) having a density of125 g/m² from Freudenberg-Politex.

The bonded fiber webs were produced by saturating the raw web with therespective impregnating liquors FK1 to FK4 and also FV1 and FV2 in thelongitudinal direction in an HVF impregnating rig with pad-mangle fromMathis (rubber roll Shore A=85°/steel roll). In each case, the wetpick-up was adjusted to 162.5 g of impregnating liquor (corresponding toa solids content of 24.4 g). The impregnated fiber webs obtained weresubsequently dried and cured in an LTV laboratory dryer with needleframe from Mathis (in circulating air operation). To this end, theimpregnated fiber webs were each placed on an open needle frame, fixedby folding shut and then dried and cured at 200° C. for 3 minutes. Thebonded fiber webs obtained in the process are signified as fiber websFK1 to FK4 and also FV1 and FV2, depending on the impregnating liquorsused.

Determination of Breaking Strength in Transverse Direction

Breaking strength in transverse direction was determined for fiber websFK1 to FK4 and also FV1 and FV2 at room temperature in accordance withDIN 52123 using a breaking machine from Frank (model 71565). In eachcase, 5 separate measurements were carried out. The measurements in N/50mm which are reported in table 1 represent the respective averages ofthese measurements. The higher the measurements, the better the breakingstrength in the transverse direction.

Determination of Heat Resistance

The heat resistance of fiber webs FK1 to FK4 and also FV1 and FV2 wasdetermined on the lines of DIN 18192 by measuring the extension in thelongitudinal direction and the shrinkage in the transverse direction at200° C. To this end, 100×340 mm strips were die-cut out of the fiberwebs in the longitudinal direction. Marks were made in the center oneach of the fiber web strips at points respectively located 120 mm awayfrom the two narrow sides, the marks defining a measuring sector of 100mm therebetween. In the middle of this measuring sector the width of thefiber web strip was checked by measurement. Thereafter, the narrow endswere clamped into clamping rails. Concurrently thereto, the tripodrequired for measurement and also a stainless steel cylinder 8 kg inweight were heated up to 200° C. in a drying cabinet. For performing thetest, then, the marked and measured fiber web strips were attached withone of the clamping rails to the tripod in the drying cabinet to hangdown freely. The 8 kg stainless steel cylinder was then suspended fromthe lower clamping rail, the door of the drying cabinet was closed andthe fiber web thus clamped was left at 200° C. in the drying cabinet for10 minutes. Thereafter, the laboratory tripod together with the weightedfiber web strip was taken form the drying cabinet and left to cool downat room temperature for 5 minutes. Thereafter, the stainless steelcylinder was taken off of the lower clamping rail and then the upperclamping rail was first taken off the tripod (the tripod and thestainless steel cylinder were put back in the drying cabinet forconditioning for the next measurement). After the upper and lowerclamping rails had been removed, the fiber web strip was laid flat onthe laboratory table and the respective distance between the two appliedmarks (in the longitudinal direction) and also the respective width atthe narrowest place (in the transverse direction) of the fiber webstrips were measured. In each case, measurements were carried out on 5separate measuring strips. The values likewise reported in Table 1represent the averages of these measurements. The lower the extension inthe longitudinal direction and the lower the shrinkage in the transversedirection, the better the results. The reported figures are the changein the longitudinal or transverse direction in percent, based on thecorresponding distances before the thermal treatment.

TABLE 1 Results for transverse breaking strength at room temperature andheat resistance at 200° C. Transverse breaking strength Heat resistanceat room at 200° C. temperature Extension Shrinkage Fiber web [in N/50mm] [in %] [in %] FV1 288 5.2 −8.0 FK1 326 4.7 −5.6 FK2 332 4.3 −5.4 FK3329 4.5 −5.7 FK4 320 4.8 −6.1 FV2 292 5.4 −8.2

It is clearly apparent from the results that the fiber webs producedwith the inventive binder compositions have improved transverse breakingstrength at room temperature and also an improved heat resistance at200° C.

We claim:
 1. An aqueous binder composition, comprising: a) at least onepolymer P comprising in polymerized form ≧0.1 and ≦15 wt % of at leastone acid-functional ethylenically unsaturated monomer, at least oneα,β-monoethylenically unsaturated C₃ to C₆ mono- or dicarboxamide, orboth (monomers A), ≧8.0 and ≦30 wt % of at least one ethylenicallyunsaturated carboxylic acid nitrile or dinitrile (monomers B), ≧0 and≦5.0 wt % of at least one crosslinking monomer having two or morenonconjugated ethylenically unsaturated groups (monomers C), ≧0 and ≦10wt % of at least one monoethylenically unsaturated silane compound(monomers D), ≧20 and ≦70 wt % of at least one ethylenically unsaturatedmonomer whose homopolymer has a glass transition temperature ≦30° C.(monomers E) and which differs from the monomers A to D, and ≧25 and≦71.9 wt % of at least one ethylenically unsaturated monomer whosehomopolymer has a glass transition temperature ≧50° C. (monomers F) andwhich differs from the monomers A to D, in polymerized form, wherein theamounts of monomers A to F sum to 100 wt %; and b) at least onesaccharide compound S, an amount of which is ≧10 and ≦400 parts byweight per 100 parts by weight of the polymer P, wherein: an overallamount of additional formaldehyde-containing binder components is <50parts by weight per 100 parts by weight of a sum of the polymer P andthe saccharide compound S; and conjugated aliphatic C₄ to C₉ dienecompounds are excluded.
 2. The aqueous binder composition according toclaim 1, wherein: the at least one monomer E is selected from the groupconsisting of an ester of vinyl alcohol and a C₁ to C₁₀ monocarboxylicacid, a C₁ to C₁₀ alkyl acrylate, a C₅ to C₁₀ alkyl methacrylate, a C₅to C₁₀ cycloalkyl acrylate, a C₅ to C₁₀ cycloalkyl methacrylate, a C₁ toC₁₀ dialkyl maleinate, a C₁ to C₁₀ dialkyl fumarate, and a mixture of atleast two thereof; and the at least one monomer F is selected from thegroup consisting of a vinylaromatic monomer, a C₁ to C₄ alkylmethacrylate, and a mixture thereof.
 3. The aqueous binder compositionaccording to claim 1, wherein the polymer P is in the form of an aqueouspolymer dispersion.
 4. The aqueous binder composition according to claim3, wherein polymer particles of the aqueous polymer dispersion have anumber average particle diameter of ≧50 and ≦400 nm.
 5. The aqueousbinder composition according to claim 1, wherein the polymer P comprisesin polymerized form ≧0.5 and ≦10 wt % of at least one monomer A, ≧10 and≦25 wt % of at least one monomer B, ≧0 and ≦1.5 wt % of at least onemonomer C, ≧0 and ≦5.0 wt % of at least one monomer D, ≧25 and ≦65 wt %of at least one monomer E, and ≧25 and ≦64.5 wt % of at least onemonomer F.
 6. The aqueous binder composition according to claim 1,wherein the polymer P comprises in polymerized form ≧3.0 and ≦8.5 wt %of acrylic acid, methacrylic acid, itaconic acid, acrylamide,methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, or amixture of at least two thereof, ≧10 and ≦20 wt % of acrylonitrile,methacrylonitrile, or a mixture thereof, ≧0 and ≦1.5 wt % of1,4-butylene glycol diacrylate, allyl methacrylate, divinylbenzene, or amixture of at least two thereof, ≧30 and ≦60 wt % of 2-ethylhexylacrylate, n-butyl acrylate, ethyl acrylate, or a mixture of at least twothereof, and ≧25 and ≦57 wt % of methyl methacrylate, styrene,tert-butyl methacrylate, or a mixture of at least two thereof.
 7. Theaqueous binder composition according to claim 1, wherein the polymer Pcomprises the monomers A, B, D, E and F and has a glass transitiontemperature of ≧15 and ≦45° C.
 8. The aqueous binder compositionaccording to claim 1, wherein the at least one saccharide compound S isselected from the group consisting of starch, cellulose, guaran,xanthan, alginate, pectin, chitosan, gum arabic gellan, and a mixture ofat least two thereof.
 9. The aqueous binder composition according toclaim 1, wherein the at least one saccharide compound S is selected fromthe group consisting of a starch, a starch derivative, a starchsubstitution product, and a mixture of at least two thereof.
 10. Theaqueous binder composition according to claim 1, wherein the saccharidecompound S has a weight average molecular weight of ≧50 000 and ≦1 000000 g/mol.
 11. The aqueous binder composition according to claim 1,comprising ≧40 and ≦250 parts by weight of the saccharide compound S per100 parts by weight of the polymer P.
 12. The aqueous binder compositionaccording to claim 1, comprising ≦10 parts by weight of the additionalformaldehyde-containing binder components per 100 parts of the sum ofthe polymer P and the saccharide compound S.
 13. A binder for granularand/or fibrous substrates, comprising the aqueous binder composition ofclaim
 1. 14. A process for producing a shaped article from granularand/or fibrous substrates, the process comprising: applying the aqueousbinder composition of claim 1 to a granular substrate, a fibroussubstrate, or a mixture of both, to form a treated substrate; optionallyshaping the treated substrate; and thermally treating the treatedsubstrate at a temperature of ≧110° C.
 15. The process of claim 14,wherein ≧1 and ≦100 g of a sum of the polymer P and the polysaccharidecompound S are applied per 100 g of the granular substrate, the fibroussubstrate, or a mixture of both.
 16. A shaped article obtained by theprocess of claim
 14. 17. The shaped article according to claim 16, whichis adapted to produce a bituminized roofing membrane.
 18. A bituminizedroofing membrane, comprising the shaped article according to claim 16.